CN105218815B - Preparation method for maleic anhydride modified graphene oxide/bismaleimide nanometer composite material - Google Patents
Preparation method for maleic anhydride modified graphene oxide/bismaleimide nanometer composite material Download PDFInfo
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- CN105218815B CN105218815B CN201510583578.9A CN201510583578A CN105218815B CN 105218815 B CN105218815 B CN 105218815B CN 201510583578 A CN201510583578 A CN 201510583578A CN 105218815 B CN105218815 B CN 105218815B
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Abstract
The invention belongs to the technical field of nanometer materials, and specifically relates to a preparation method for a maleic anhydride modified graphene oxide/bismaleimide nanometer composite material. The method comprises the following steps: subjecting graphene oxide to surface modification in a solvent by using maleic anhydride, then introducing double-bond groups capable of chemically reacting with a resin matrix onto the surface of graphene oxide, then adding maleic anhydride modified graphene oxide into liquid O,O'-diallyl bisphenol A (DBA), carrying out ultrasonic dispersion and then adding bismaleimide diphenylmethane resin (BDM), and carrying out reaction so as to generate graphene modified bismaleimide resin nanometer composite material. The nanometer composite material prepared by using the method in the invention can effectively improve toughness and strength of bismaleimide resin, so comprehensive performance of the bismaleimide composite material is further improved. The nanometer composite material prepared by using the method in the invention can be extensively applied in a plurality of fields of aerospace, automobile, ships, mechanical electronics, etc., and is convenient for industrial application of graphene.
Description
Technical field：The present invention relates to graphene oxide/BMI the nano composite material of maleic anhydride modification
Preparation method, belong to technical field of nano material.
Background technology：BMI（BMI）It is to be derived to form by polyimide resin system, and with maleimide
For the bifunctional compound of active end group, its as advanced composite material main base resin, with good heat resistance
Energy and mechanical property.Because BMI resins show the advantage and potentiality of uniqueness in aerospace field, therefore it is considered as boat
The important symbol of empty space material technological progress.But unmodified BMI resins its main deficiencies is self-curing thing due to fragility
Greatly, poor toughness, seriously constrains its application in high-tech sector.
With O, O '-diallyl bisphenol（DBA）Modified 4,4 '-dimaleoyl imino diphenyl-methane（BDM）Resinite
Although system achieves good toughening effect, but still can not reach the level of high tenacity resin.At present, using inorganic nano material
Polymeric matrix is modified and has been considered as a kind of practicable effective ways.Graphene is the two dimension of monoatomic thickness
Carbon atom crystal, it is considered to be the basic structural unit of fullerene, CNT and graphite.Because Graphene has excellent power
Performance, hot property and great specific surface area are learned, is compared with more with other Nano fillings when thus be accordingly used in polymer modification
Obvious advantage.
Graphene has higher draw ratio and specific surface area, is affected easily to roll into a ball by Van der Waals force and surface energy
It is poly-, and be difficult compatible with organic polymer.There are a large amount of oxy radicals in graphene oxide structure, provide for its surface modification
On the one hand abundant reactivity point, surface modification can make Graphene be changed into lipophile from hydrophily, on the other hand can effectively prevent
The only generation of agglomeration, these two aspects is conducive to increasing Graphene and polymer compatibility therebetween, so as to improve
Modified effect to polymer.
" preparation method of Graphene modified bismaleimide resin nano composite material " of Tongji University's application（Patent
Number be 201110204405.3）Disclose a kind of preparation side of Graphene modified bismaleimide resin nano composite material
Method, by Graphene after carboxylated, chloride, then in its diamine of introducing with feature structure or polyamine, Ran Houli
Addition reaction is carried out with this amidized Graphene and BMI, the modified bimaleimide resin of Graphene is generated
Nano composite material.The patent is disclosed is the Graphene for containing amino using surface is carried out to bimaleimide resin
The modified method for preparing nano composite material, does not relate to the graphene oxide of maleic anhydride modification as BMI
The modifying agent of resin, is also not involved with the curing reaction that double bond contained in maleic anhydride participates in bimaleimide resin.
" hyperbranched polyorganosiloxane graft grapheme/Bismaleimide composites and the preparation method " of Northwestern Polytechnical University's application
（Patent No. 201210282214.3）Disclose a kind of hyperbranched polyorganosiloxane graft grapheme modified bismaleimide to receive
The preparation method of nano composite material, Graphene, the 100 parts of diphenyl-methane type spans that 0.1-10 parts hyperbranched polyorganosiloxane is modified
Come acid imide and the mixing of 10-100 parts bisphenol a diallyl ether, nano composite material is prepared using casting moulding.The patent
Disclosure of that is the method that the Graphene modified using hyperbranched polyorganosiloxane is modified to bimaleimide resin,
Also without be related to maleic anhydride modification graphene oxide as bimaleimide resin modifying agent in terms of content.
The content of the invention
The present invention is to further improve O, O '-diallyl bisphenol（DBA）Modified bismaleimide resin base is answered
The performance of condensation material, and the Graphene of the utilization maleic anhydride modification for providing is modified preparation and receives to bimaleimide resin
The method of nano composite material.
For achieving the above object, the technical solution used in the present invention is：Graphite alkene/the span of maleic anhydride modification carrys out acyl
The preparation method of imine nanometer composite, its step is as follows：In a solvent, table is carried out to graphene oxide using maleic anhydride
Face is modified, and introducing in surface of graphene oxide can carry out the double bond group of chemical reaction with resin matrix, then by maleic anhydride
The graphene oxide of modification is added to the O of liquid, O '-diallyl bisphenol（DBA）In, Jing after ultrasonic disperse, add span to come
Imide diphenyl-methane resin（BDM）Reacted, generated the modified nano combined material of bimaleimide resin of Graphene
Material.The chemical substance structure of the graphene oxide of maleic anhydride modification is as shown in Figure 1.
Described graphene oxide refers to that graphite is obtained Jing after the oxidation of the strong oxidizers such as the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate
Surface contain the graphene sheet layer of the groups such as hydroxyl, carboxyl, epoxy radicals.
Maleic anhydride can be generated in maleic acid, therefore described step 1 and added also known as maleic anhydride, hydrolysis
Maleic anhydride could alternatively be maleic acid.
Described solvent is N,N-dimethylformamide, tetrahydrofuran or 1-METHYLPYRROLIDONE.
The beneficial effect that reached of the present invention is：In O, O '-diallyl bisphenol（DBA）/ 4,4 '-BMI
Base diphenyl-methane resin（BDM）In system, by the graphene oxide for introducing maleic anhydride modification, the impact of nano composite material
Intensity, tensile strength, stretch modulus, bending strength and bending modulus are respectively increased 30-100%.Obtained BMI tree
Resin nano composite material, excellent combination property has broad application prospects.
Description of the drawings：
Fig. 1：The chemical substance structure of the graphene oxide of the maleic anhydride modification obtained in step 1.
Specific embodiment
Embodiment 1
Step 1：Under 50 DEG C of water bath condition, in adding graphene oxide into solvent DMF, enter
The ultrasonic disperse of row 1.5h, the power of ultrasonic disperse is 1000W, and frequency is 40Hz；It is subsequently adding the quality with graphene oxide
Than for 1:500 maleic anhydride reaction 3h, after being cooled to room temperature, with absolute ethanol washing, removes wherein unreacted maleic acid
Acid anhydride, then Jing vacuum freeze dryings obtain maleic anhydride modification graphene oxide；
Step 2：Under the conditions of 80 DEG C of oil bath, the graphene oxide that maleic anhydride is modified is added to into O, the allyls of O '-two
Base bisphenol-A（DBA）In, the ultrasonic disperse of 1.5h is carried out, ultrasonically treated power is 1000W, and frequency is 40Hz；Then add
Dimaleoyl imino diphenyl-methane resin（BDM）The amount ratio for carrying out the material of the pre-polymerization of 0.5h, DBA and BDM is 1.15:1, horse
The consumption for carrying out the graphene oxide of acid anhydrides modification is the 10% of dimaleoyl imino diphenyl-methane resin quality；
Step 3：The performed polymer that step 2 is obtained, in being poured into the mould of preheating, in being put into 130 DEG C of vacuum drying oven, takes off
It is put into air dry oven after bubble removing to be solidified, curing process is followed successively by under 140 DEG C of temperature conditionss and solidifies 1h, 180 DEG C of temperature
Under the conditions of solidify 2h, 1h is solidified under 220 DEG C of temperature conditionss, solidify 6h under 250 DEG C of temperature conditionss, natural cooling after solidification；It is natural
After cooling, the demoulding is obtained the graphene oxide/BMI nano composite material of maleic anhydride modification.
Embodiment 2
Step 1：Under 95 DEG C of water bath condition, in adding graphene oxide into solvents tetrahydrofurane, the super of 1h is carried out
Sound disperses, and the power of ultrasonic disperse is 100W, and frequency is 15Hz；It is 1 to be subsequently adding with the mass ratio of graphene oxide:1 it is suitable
Butene dioic acid reacts 0.5h, after being cooled to room temperature, with absolute ethanol washing, removes wherein unreacted maleic acid, then
Jing vacuum freeze dryings obtain the graphene oxide of maleic acid modification；
Step 2：Under the conditions of 130 DEG C of oil bath, the graphene oxide that maleic acid is modified is added to into O, O '-diene
Propyl group bisphenol-A（DBA）In, the ultrasonic disperse of 1h is carried out, ultrasonically treated power is 100W, and frequency is 15Hz；Then add
Dimaleoyl imino diphenyl-methane resin（BDM）The amount ratio for carrying out the material of the pre-polymerization of 0.5h, DBA and BDM is 1.15:1, it is suitable
The consumption of the graphene oxide of butene dioic acid modification is the 1% of dimaleoyl imino diphenyl-methane resin quality；
Step 3：The performed polymer that step 2 is obtained, in being poured into the mould of preheating, in being put into 60 DEG C of vacuum drying oven, takes off
It is put into air dry oven after bubble removing to be solidified, curing process is followed successively by under 140 DEG C of temperature conditionss and solidifies 1h, 180 DEG C of temperature
Under the conditions of solidify 2h, 1h is solidified under 220 DEG C of temperature conditionss, solidify 6h under 250 DEG C of temperature conditionss, natural cooling after solidification；It is natural
After cooling, the demoulding is obtained the graphene oxide/BMI nano composite material of maleic acid modification.
Embodiment 3
Step 1：Under 75 DEG C of water bath condition, in adding graphene oxide into tetrahydrofuran, the ultrasound of 1.25h is carried out
Dispersion, the power of ultrasonic disperse is 500W, and frequency is 25Hz；It is 1 to be subsequently adding with the mass ratio of graphene oxide:200 horse
Carry out anhydride reaction 2h, after being cooled to room temperature, with absolute ethanol washing, remove wherein unreacted maleic anhydride, then Jing vacuum
Freeze-drying obtains the graphene oxide of maleic anhydride modification；
Step 2：Under the conditions of 100 DEG C of oil bath, the graphene oxide that maleic anhydride is modified is added to into O, the allyls of O '-two
Base bisphenol-A（DBA）In, the ultrasonic disperse of 1.25h is carried out, ultrasonically treated power is 500W, and frequency is 25Hz；Then add
Dimaleoyl imino diphenyl-methane resin（BDM）The amount ratio for carrying out the material of the pre-polymerization of 0.5h, DBA and BDM is 1:1, Malaysia
The consumption of the graphene oxide of acid anhydrides modification is the 5% of dimaleoyl imino diphenyl-methane resin quality；
Step 3：The performed polymer that step 2 is obtained, in being poured into the mould of preheating, in being put into 100 DEG C of vacuum drying oven, takes off
It is put into air dry oven after bubble removing to be solidified, curing process is followed successively by under 140 DEG C of temperature conditionss and solidifies 1h, 180 DEG C of temperature
Under the conditions of solidify 2h, 1h is solidified under 220 DEG C of temperature conditionss, solidify 6h under 250 DEG C of temperature conditionss, natural cooling after solidification；It is natural
After cooling, the demoulding is obtained the graphene oxide/BMI nano composite material of maleic anhydride modification.
Embodiment 4
Step 1：Under 65 DEG C of water bath condition, in adding graphene oxide into 1-METHYLPYRROLIDONE, 1.3h is carried out
Ultrasonic disperse, the power of ultrasonic disperse is 600W, and frequency is 30Hz；It is 1 to be subsequently adding with the mass ratio of graphene oxide:
300 maleic anhydride reaction 1.5h, after being cooled to room temperature, with absolute ethanol washing, removes wherein unreacted maleic anhydride, so
The graphene oxide of maleic anhydride modification is obtained by vacuum freeze drying；
Step 2：Under the conditions of 120 DEG C of oil bath, the graphene oxide that maleic anhydride is modified is added to into O, the allyls of O '-two
Base bisphenol-A（DBA）In, the ultrasonic disperse of 1.2h is carried out, ultrasonically treated power is 800W, and frequency is 30Hz；Then add
Dimaleoyl imino diphenyl-methane resin（BDM）The amount ratio for carrying out the material of the pre-polymerization of 0.5h, DBA and BDM is 1:1, Malaysia
The consumption of the graphene oxide of acid anhydrides modification is the 8% of dimaleoyl imino diphenyl-methane resin quality；
Step 3：The performed polymer that step 2 is obtained, in being poured into the mould of preheating, in being put into 120 DEG C of vacuum drying oven, takes off
It is put into air dry oven after bubble removing to be solidified, curing process is followed successively by under 140 DEG C of temperature conditionss and solidifies 1h, 180 DEG C of temperature
Under the conditions of solidify 2h, 1h is solidified under 220 DEG C of temperature conditionss, solidify 6h under 250 DEG C of temperature conditionss, natural cooling after solidification；It is natural
After cooling, the demoulding is obtained the graphene oxide/BMI nano composite material of maleic anhydride modification.
Claims (4)
1. maleic anhydride modification graphene oxide/BMI nano composite material preparation method, it is characterised in that
Comprise the following steps that：
Step 1：Under 50-95 DEG C of water bath condition, in adding graphene oxide into solvent, the ultrasound point of 1-1.5h is carried out
Dissipate, the power of ultrasonic disperse is 100-1000W, and frequency is 15-40Hz；It is 1 to be subsequently adding with the mass ratio of graphene oxide:1-
500 maleic anhydride, after reaction 0.5-3h, is cooled to room temperature, and uses absolute ethanol washing, removes wherein unreacted maleic acid
Acid anhydride, then Jing vacuum freeze dryings obtain maleic anhydride modification graphene oxide；
Step 2：Under the conditions of 80-130 DEG C of oil bath, the graphene oxide that maleic anhydride is modified is added to into O, the allyls of O '-two
Base bisphenol-A（DBA）In, the ultrasonic disperse of 1-1.5h is carried out, ultrasonically treated power is 100-1000W, and frequency is 15-40Hz；
Then dimaleoyl imino diphenyl-methane is added（BDM）Resin carries out the amount ratio of the material of the pre-polymerization of 0.5h, DBA and BDM
For 0.85-1.15:1, the consumption of the graphene oxide of maleic anhydride modification is dimaleoyl imino diphenyl-methane resin quality
1-10%；
Step 3：The performed polymer that step 2 is obtained, in being poured into the mould of preheating, in being put into 60-130 DEG C of vacuum drying oven, takes off
It is put into air dry oven after bubble removing to be solidified, curing process is followed successively by under 140 DEG C of temperature conditionss and solidifies 1h, 180 DEG C of temperature
Under the conditions of solidify 2h, 1h is solidified under 220 DEG C of temperature conditionss, solidify 6h under 250 DEG C of temperature conditionss, natural cooling after solidification；It is natural
After cooling, the demoulding is obtained the graphene oxide/BMI nano composite material of maleic anhydride modification.
2. graphene oxide/BMI nano composite material that maleic anhydride according to claim 1 is modified
Preparation method, it is characterised in that：Described graphene oxide refers to the graphite Jing concentrated sulfuric acids, red fuming nitric acid (RFNA) or potassium permanganate strong oxidizer
Contain the graphene sheet layer of hydroxyl, carboxyl or cycloalkyl groups in the surface obtained after oxidation.
3. graphene oxide/BMI nano composite material that maleic anhydride according to claim 1 is modified
Preparation method, it is characterised in that：The maleic anhydride added in described step 1 replaces with maleic acid.
4. graphene oxide/BMI nano composite material that maleic anhydride according to claim 1 is modified
Preparation method, it is characterised in that：Described solvent is N,N-dimethylformamide, tetrahydrofuran or 1-METHYLPYRROLIDONE.
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